DE2824710A1 - HYDRO-INSOLUBLE MONOAZO DYES - Google Patents

Description

282A710

Our no. 21 96O Pr / br

Aziende Colori Nazionali Affini ACNA Spa.

Milan / Italy

Water-insoluble monoazo dyes

The invention relates to new monoazo dyes which are insoluble in water and are free of hydrosolubilizing groups and are derived from 4-aminothiazole of the following general formula:

N C - N = N-Y

: -r '■ (i)

where R and R ^{1 can be} identical or different and represent a cyano radical or an optionally substituted carbalkoxyl radical with 2 to 8 carbon atoms (COOCH ₃ , COOC ₄ H ₉ , COOCH ₂ CH ₂ OCH ₂ CH ₂ OCh or COOCH ₂ CH ₂ Cl) and Y is the remainder of a coupling base, namely a derivative of l-phenyl-5-aminopyrazole, l-phenyl-5-hydroxypyrazole, indole, N-monoalkyl- or Ν, Ν-dialkylaminobenzene, N ~ monoalkylaminonaphthalene or N, N-dialkylaminonaphthalene or Mean 6-hydroxy-2-pyridone.

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The following should be mentioned as examples of the coupling components (Y-H):

1- (p-Tolyl) -5-aminopyrazole 1- (p-Tolyl) -3-methyl-5-aminopyrazole 1-phenyl ^ -methyl-S-hydroxypyrazole l- (m-Chlorophenyl) -5-hydroxypyrazole l-Cm-ChlorophenylJ-S-methyl-ij-hydroxypyrazole 1-phenyl-S-carbomethoxy-S-hydroxypyrazole 1-methyl-2-phenylindole (3'-methoxy-4'-hydroxy) -2-phenylindo}.

1- (2'-cyanoethyl) -2-phenylindole 1- (3'-hydroxypropyl) -2-phenylindole N-ß-acetoxyethyl-N-ß-cyanoethylaminobenzene N-ethyl-N-ß-cyanoethylaminobenzene Ν, Ν-diethyl-m-acetylaminoaminobenzene N, N-dimethyl-m- (ß-carbomethoxypropionyl) aminobenzene 1-diethylaminonaphthalene or 1-phenethylaminonaphthalene Derivatives of 6-hydroxy-2-pyridone of the general formula

^R 2 R.

(III)

wherein R _{1 is} CN, COO-alkyl, CO-alkyl, CO-NH-alkyl, CO-N- (alkyl) ₂ or

CO-N

where X is O or CH ₂ , η 1 or 2, m 1 or 2 and m + η 3 or and the alkyl groups have 1 to 8 carbon atoms,

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Rp optionally substituted alkyl has 1 to 8 carbon atoms, a heterocyclic group or an aromatic group with 6 to 10 carbon atoms and R, an optionally substituted alkyl, cycloalkyl with 5 to 8 carbon atoms or aryl with 6 to 10 carbon atoms Atoms, - (CH ₂ ), - 0-alkyl, - (CH ₂ ) -0- (CH ₂ ) ^ O-alkyl, -NH ₃ , -NH-alkyl, -N- (alkyl) ₂ or

wherein χ ο or CH ₂ , η 1 or. 2, m 1 or 2 and m + η 3 or 4, where the alkyl groups have 1 to 8 carbon atoms.

The new dyes are particularly suitable in finely divided form for dyeing textile materials such as fibers, yarns, Staple fibers, woven and knitted fabrics made from linear polyester, polyamides or secondary or tertiary cellulose acetate.

The resulting colorations are generally good Stabilities and a high staining intensity, and in In most cases they are suitable for achieving white and colored etching effects using the "alkali reserve" method.

The new dyes are made by diazotizing the derivatives of 4-aminothiezole of the formula

-NH ₂

(ID R ¹

R -CH ₂

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and produced by coupling with a coupling component Y-H.

The 4-aminothiazoles (II) described herein and used as diazotizing amines are prepared according to known methods. Wobig, dear Ann Chem. 764: 125-130 (1972); W. Walek et al, Tetrahedron 32, 623-627 (1976) _7, starting from carbon disulfide, KOH, cyanamide and chloroacetonitrile (or an alkyl chloroacetate):

KS

2K0H + CS + ₀ NH_CN -1> C = N-CN + 2HO

KS

KS + 2 AIgCH ₂ R -2KAIg N - | " ^NH 2

K-S

\ ° 2 ti

C = N-C = N +: E> g / '

/ cat. N (C, H) I

-50 _{CH R}

where R and R ^{f have the} preceding meaning and AIg is chlorine, bromine or iodine.

The coupling components YH are prepared by known processes, for example N-methyl-3-cyano-4-methyl-6-hydroxy-2-pyridone (formula III, where R ₁ = CN, R ₂ and R 1 = CH) ) by heating ethyl acetate, ethyl cyanoacetate and methylamine (Guareschi, Zentralblatt 1907, I 875).

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The following examples serve to further illustrate the invention. Unless otherwise stated, denotes parts Parts by weight.

example 1

3.93 parts of II (R = R = COOCH,) were added with stirring at 0 to 5 C within 30 minutes to a mixture of 30 parts by volume of acetic acid, 15 parts by volume of propionic acid and 7.5 parts by volume of a 2N solution of NOHSO ^ in concentrated H- SO ^ added. Stirring was continued at 0-5 ° C for 1 hour. The resulting dxazonium salt solution was treated with sulfamic acid to remove the existing NOHSO ₂ . treated and at 0 to 5 ° C to a solution of 2.8 parts of l- (p-tolyl) -3-methyl-5-aminopyrazole, dissolved in 100 parts by volume of acetic acid, added, with sodium acetate crystals to a pH of 4 to 5 has been buffered.

After stirring for 30 minutes at 0 to 5 ° C, the whole was poured into water, the resulting precipitate was filtered and Washed until neutral mother fluids are obtained became. It was dried in the oven under vacuum at 60 ° C., yielding 5.6 parts of a dye of the following formula received:

H COOC-iH

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. * ΐ 1 mm

The IR spectrum showed two bands of the COOCH groups, at 1700 and 1738 cm " ¹ .

The dye was made into a microfine liquid with about 1.5 parts by volume of ethylene glycol and about the same weight of Saltra SS (condensate of formaldehyde, m- and p-cresol and Schaffer's acid) and 87 parts of water.

100 parts of the aforementioned liquid microfine dye were with 150 parts Lamitex LlO (a thickener based on sodium alginate), 2 parts of sodium chlorate, 3 parts of citric acid and 745 parts of water. The liquid thus obtained was used to swab a polyester fabric.

After drying at 80 to 90 ⁰ C, the fabric was printed with a paste for Weißätzen, 90 parts of sodium bicarbonate, 66 parts of polyethylene glycol, 33 parts of glycerine, 400 parts Lamitex LLO, 210 parts of water and 200 parts of an emulsion containing 80% White spirit, 6 % emulsifier Diphasol EV ^V (based on a long-chain condensate of ethylene oxide with a branched C ₁ / - to C ₁ Q-AlkOhOl) and 14 % water.

It was then ^{evaporated at 170 °} C. for 8 to 10 minutes. After washing and reducing cleaning with NaOH (4 g / l) and hydrosulfite (2 g / l) at 70 to 8O ⁰ C a bright yellow color was obtained with an intensity of about 1/3 of ECE, which in the etched zones perfectly white was.

The same observation regarding etchability could be made using 400 parts of the liquid microfine Dye. In this case the coloration was about 1/1 E.C.E. The dyeings showed good stabilities to sublimation and wet washing and excellent fastness to sunlight. That for the synthesis of the dye Aminothiazole (II) R = R '= COOCH used in Example 1 was prepared as follows:

8 09851/0806

76 parts of CS ₂ and 42 parts of cyanamide dissolved in 75 parts by volume of methanol were placed in a reactor equipped with a stirrer, a condenser and a thermometer. 113 parts of KOH, dissolved in 350 parts by volume of methanol, were then added, making sure that the temperature did not exceed 25.degree. After stirring for an additional 30 minutes, 200 parts of methyl chloroacetate were added and the mixture was refluxed for 1 hour. It was cooled to 50 ⁰ C, 21 parts by volume of triethylamine were added and it was heated for 15 minutes under reflux. l60 parts by volume of methanol was distilled off, then was cooled to 5 to 10 ⁰ C and the solid precipitate filtered off. The latter was dispersed in 3,000 parts of water and stirred for 60 minutes at room temperature, filtered again and dried in the oven under vacuum at 60.degree.

127 parts of a product were obtained having a melting point of 98 to 100 ⁰ C, had the following IR spectra: two COOCH-r-bands at I668 and 1735 cm ^"1, the primary NH ₂ at 3290 and 3460 cm" ¹ and the Thiazole ring at 1300, 138C and 1520 cm " ¹ .

Example 2

Under the same conditions as in Example 1 with the same 4-aminothiazole (II) (R = R ¹ = COOCH ^) in an amount of 5.24 parts and with 10 parts by volume of a 2N solution of NOHSO ₁₄ in concentrated H. ₂ SO ^ a solution of the diazonium salt of the above-mentioned thiazole was obtained. This solution was added with stirring at 0 to 5 ° C a ⁰ to 5 C, cooled to 0 solution of 4.14 parts of 2-phenyl-l-methyl-indole, which had previously been dissolved hot in 100 VoI.-parts of acetic acid is added . During the addition, the pH was adjusted by adding sodium acetate

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held at ¹ I to 5. After stirring for 30 minutes at 0 to 5 ° C, the reaction mass was poured into water, filtered, the resulting precipitate was washed until the mother liquor was neutral and then dried in the oven under vacuum at 60 ° C. 8.6 parts of a dye of the following formula

N "N ~ N__

S ^

CH CQQCH ^ " CH
2 3 3

which had two bands of COOCH, at 1710 and 1739 cm ", were received.

The same effects of white etching were achieved by the Alkaliätζverfahren described in Example 1 with the same microfine liquid applied.

The colorations showed a bright golden yellow tone and exhibited good stabilities to sunlight, sublimation and wet washing.

Using the ^ -aminothiazoles and coupling components given in the table below instead of those given in the previous examples, dyes with similar properties were obtained.

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Example 4-amino game thiazole No. (II)

Coupling component

Shade of polyester

R = COOCH

R'-COOCH HO

-CH

yellow

RF COOCH.

R'-COOCH

R = COOCH,

R '= COOC " R = COOCH

R ** = COOCH,

R-CIi R * = CN

. (R β CH '

R »- CN · ■ HO

CH.

N '
ι

Cl

CH CM / 24

NHCOCH

CH.

N
O

CH.

H CN

2 4

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yellow

orange

Red

yellow

orange

Example 4-amino game thiazole No. (II)

Coupling component

Shade of polyester

J R * * CH ]
R ' = CH (R - = ■ CM (R ' - CM • f R => CH Rl «CH

V—./

3 2

I COOCH

NHCOCH

purple red

violet

violet

Example 12

3.93 parts of 4-aminothiazole II (R = R '= COOCH ₃ ) were suspended by stirring in a mixture of 20 parts by volume of acetic acid and 10 parts by volume of propionic acid.

After cooling to 0 to 5 ° C., 3.75 parts by volume of 4N nitrosylsulfuric acid were obtained in concentrated H_S0k within 30 minutes constantly added with stirring.

The diazonium salt solution prepared in this way was at 5 to 10 ° C and at a pH of 4 to 5, which had been adjusted by adding hydrated sodium acetate, a suspension of a compound of the formula III (R ₁ = CN, R ₃ = R ₃ = CH ₃ ), which had been prepared by dissolving 2.62 parts of coupling agent in 127 parts of 6.3 strength NaOH and precipitating with 25 parts of CH ₃ COOH, was added. Filtering and washing gave 6 parts of a yellow dye of the formula

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T I I S. H C CN 282A710 II λΤ V_ / / ^{= 0} rum zeißt i> - ^CH 3 \ HO
COOCH
3 H COOC-CH ^ e two bands of COOCH -, - ( obtain.
The IR spect JruDDen at

—1 —1

1690 and 173O cm and a band of a C = O group at 1650 cm.

Two parts of the above dye were micronized with 64.7 parts of a solution of 3.9% Chemitrol 1 (sodium lignosulfonate), 10.3 % ethylene glycol and 85.8 % water.

200 parts of the aforementioned microfine liquid were mixed with 100 parts of Lamitex L 10 · (a thickener based on sodium alginate), 2 parts of sodium chlorate,

3 parts of citric acid and 695 parts of water mixed.

The resulting liquid was used to flap a polyester fabric. After drying at 80 to 90 ° C., the fabric was printed with a white etching paste containing 90 parts of sodium bicarbonate, 66 parts of polyethylene glycol, 33 parts of glycerine, 400 parts of Lamitex L 10, 210 parts of water and 200 parts of an emulsion containing 80 % White spirit, 6 % of an emulsifier Diphasol EV (consisting of a long-chain condensate of ethylene oxide with a branched CLg-CLo alcohol) and 14 % water.

This was followed by steaming at 170 ° C. for 8 to 10 minutes. After washing and reducing cleaning with 4 g NaOH / liter and 2 g hydrosulphite / liter at 70 to 80 ° C became a luminous yellow. \

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Color obtained that has an intensity of about 1/1 E.C.E, with the etched areas being perfectly white. The same observation regarding etchability could be made are made using 400 parts of the microfine liquid. The dyeings showed good stabilities to sublimation, wet washing and sunlight.

Example 13

Example 12 was followed using the same 4-amxnothiazole II (R = R ¹ = COOCH ₃ ) with the difference that pyridone of the formula III was used, in which R ₁ = CN, Rp = CH, and Rz = C ₂ Hf - meant. 6.2 g of a yellow dye of the formula were obtained

ν - J COOCH K CN
S i · '* N- Γ
r>
HO / ^ ⁰ · ■■ II I. H COOC-CH

The IR spectrum showed two bands of COOCH, groups

Jt £ r \ r \ j * 4 »It / s * λ _ ·« 3_ j rt r \ / t t_ _ ^ * f ^ Ί · "* ^

at

1690 and 1740 cm "" ¹ "and a band of the C = 0 group at 1645 cm. The same white etching effects were obtained by carrying out the alkali etching process described in the example with an identical microfine liquid by using either 100 g / l, 200 g / l or 400 g / l printing paste worked The dyeings showed a bright yellow shade and good stabilities to sunlight, sublimation and wet washing.

For: Aziende Colori Nazionali Affini ACNA S.p.A. Milan, Italy

Lawyer

Claims (5)

BEIL, WOLFF & REfL ftc, lawyers ° June 5, 1978 ADELONSTRAS3E 58 FRANKFURT AM MAIN 80 2824710 Patent claims: 1. Monoazo dye of the general formula N C -N = N-Y CR ¹ CH ₂ R wherein R and R 'can be the same or different and one Cyano group or a carbalkoxyl group with 2 to 8 carbon atoms and Y the remainder of a coupling base, namely a derivative of l-phenyl-5-aminopyrazole, l-phenyl-5-hydroxypyrazole, Indole, N-monoalkyl or Ν, Ν-dialkylaminobenzene, N-monoalkyl or Ν, Ν-dialkylaminonaphthalene or 6-hydroxy-2-pyridone. 2. Dye according to claim 1 of the formula N N = N- XJ '{I ° ^H 2 ^R (ά- a wherein a is H or CH ₃ , b is H or CH ₃ and R and R ^{1 are} CN or COO-C ₂ -Cg-alkyl. 809851/0806 ORIGINAL INSPECTED 3. Dyestuff according to claim 1 of the general formula N; π-N = N CH ₀ R (83 "» and
where c is Cl or Br / η 1 to 2, or η 0 and _{c is} H. d is CH, COO-C ₁ -C _{6 -alkyl, CONH 2} , CH ₂ COO-C _{1 -C 1} J-alkyl or CH ₂ CONHCgH and R and R ^{1 are} CN or COO-C 1 -C 6 -alkyl. 4. Dye according to claim 1 of the general formula ^N , i Γ ^{Ν = N} wherein e is an unsubstituted or substituted by OH and / or C.-C. _1-alkoxy phenyl, H or optionally substituted by OH, CN or COO-C ₁ -C f, _- alkyl substituted C ^ C ^ alkyl, and R and R ¹ CN or COO-C ^ Cg-alkyl. 5 · Dyestuff according to Claim 1 of the general formula N T ^N r ^ ¹ 809851/0806 282A710 _{wherein R is a C 1} -C 4 alkyl which is optionally substituted by OH, OC _{1 -C 11} -alkyl, 0-C0-C 1 -C 11 -AlCyI, C0-0-C ₁ -C _2i -alkyl, Cl, Br or CN , Benzyl, phenyl or (CHg) ₂ OCONHC ₂ H, R ₂ H, an optionally substituted by OH, OC ₁ -C ₄ alkyl, 0-C0-C 1 -C 1 ^ -alkyl, CO-0-C ^ C ^ -alkyl, OCOOCH ₃ , Cl, Br or CN-substituted C ^ C ^ -alkyl or (CH ₃ J ₂ OCONHC ₂ H ₅ , g is a C ₁ -C ₄ -alkyl, OC ^ C ^ -alkyl, Cl, Br, OCH ₂ CN, OCH ₂ CONH ₂ , OCH ₂ COOCH, NH (CH ₂ ) ₂ CN, NHCO-C ^ C ^ alkyl, NHCOCgH ₅ , NHCO-CH ₂ CH ₂ COO-C ₁ -C _li -alkyl, NHCONH-C ₁ -C _{1 |} -alkyl, NHCONHC ₆ H ₅ or NHSO ₂ CH, h H, O-Cj ^ -C ^ -alkyl or CH ₅ and R and R ^{1 are} CN or COO - ^ - Cg-alkyl. 6. Dyestuff according to claim 1 of the general formula _N Il II wherein R ₃ is an optionally substituted phenyl ^C l ~ ^C ~ 2 ^{alkyl »R} 4 ^H> C ₁ -C ₄ -A ^ yI or -phenyl, and R and R 'is CN or COO - Cg-älkyl mean - ^. 7. Dyestuff according to claim 1 of the general formula ¹ I. -N - N R-CH 809851/0806 wherein R and R ^{1 have} the meaning given in claim 1, R _{1 is} CN or COO-alkyl, CO-alkyl, CONH-alkyl or CON-dialkyl or optionally form a heterocyclic 5- or 6-membered ring with the N atom , Rp an optionally substituted alkyl, a heterocyclic ring or an aryl, R, an optionally substituted alkyl, cycloalkyl or aryl, (CH _o ), 0-alkyl, (CH _o ), 0 (CH _o ) _0-alkyl, » 23 " 23 2 2 Amino, monoalkylamino or dialkylamino or optionally form a 5- to 6-membered heterocyclic ring with the N atom, the number of C atoms of R ₁ and in the case of alkylene 1 to 8, in the case of Cycloalkylene is 5 to 8, and 6 to 10 in the case of arylene. 8 “Dye according to claim 7 of the general formula K- wherein R and R ^{1 are} CN or COO-C 1 -C 6 -alkyl, R _{3 is} CH and R is alkyl. 9i dye according to claim 8 of the formula . I. S ₃ COOC-H ₂ C H-C CN 3 \ / - COOCH ₃ OH 809851/0806 10. Dye according to claim 8 of the formula £ COOC-H C ι 1 3 CN "3 11. Process for the preparation of the monoazo dyes according to Claim 1, characterized in that the diazo component is used of an amine of the general formula -KH ₂ - R « wherein R and R ^{1 can be the} same or different and have the meaning given in claim 1, couples in an acidic medium with a coupling component HY, where HY has the meaning given in claim 1. 12. Textile materials made of polyester fibers, polyamides or secondary or tertiary cellulose acetate, containing the Dyes according to any one of the preceding claims. 809 851/0806